EP0213799B1 - Absorbierende Polymere, deren Herstellung und Verwendung - Google Patents

Absorbierende Polymere, deren Herstellung und Verwendung Download PDF

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Publication number
EP0213799B1
EP0213799B1 EP86306076A EP86306076A EP0213799B1 EP 0213799 B1 EP0213799 B1 EP 0213799B1 EP 86306076 A EP86306076 A EP 86306076A EP 86306076 A EP86306076 A EP 86306076A EP 0213799 B1 EP0213799 B1 EP 0213799B1
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EP
European Patent Office
Prior art keywords
monomer
weight
polymer according
carbon atoms
polymer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP86306076A
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English (en)
French (fr)
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EP0213799A1 (de
Inventor
David Farrar
Peter Flesher
Malcolm Hawe
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Ciba Specialty Chemicals Water Treatments Ltd
Original Assignee
Allied Colloids Ltd
Ciba Specialty Chemicals Water Treatments Ltd
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Priority claimed from GB858520218A external-priority patent/GB8520218D0/en
Application filed by Allied Colloids Ltd, Ciba Specialty Chemicals Water Treatments Ltd filed Critical Allied Colloids Ltd
Publication of EP0213799A1 publication Critical patent/EP0213799A1/de
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42—Use of materials characterised by their function or physical properties
    • A61L15/60—Liquid-swellable gel-forming materials, e.g. super-absorbents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/32—Polymerisation in water-in-oil emulsions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F246/00—Copolymers in which the nature of only the monomers in minority is defined
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/10—Polymers characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/14—Water soluble or water swellable polymers, e.g. aqueous gels

Definitions

  • a continuous phase of an aqueous medium can be thickened by the presence of high molecular weight synthetic polymers either in solution or in the form of swollen, very small, particles (generally below 2 J.Lm dry size). If the polymers are in solution the thickening is conventionally probably due to entanglement of polymeric chains. If the polymers are swollen and insoluble the thickening is probably due to interparticulate attraction and solvent immobilisation.
  • thickening of a continuous aqueous phase can be improved in some instances by including in the polymer pendant hydrophobic groups.
  • an additional effect occurs within the continuous phase that gives the improved properties, and this additional effect is believed to be association within the aqueous phase between the hydrophobic groups in adjacent molecules.
  • the polymers containing such groups are often referred to as associative thickeners.
  • hydrophobic groups are introduced as a polymerisation initiator or chain transfer agent in the polymerisation of acrylamide.
  • the hydrophobic group is introduced as a substituent in acrylamide.
  • the pendant hydrophobic group is introduced as a vinyl ether.
  • Conventional water absorbent polymer particles for such purposes have a size greater than 20 11m and are made by polymerisation of water soluble ethylenically unsaturated monomer, often acrylic acid and/or acrylamide, in the present of cross-linking agent to prevent dissolution, minimise tackiness, and control absorptive capacity.
  • An absorbent polymer according to the invention comprises water insoluble, water-swellable particles at least 20 11m in size and is formed from (a) 30 to 99% water soluble ethylenically unsaturated monomer, (b) 0 to 40% water insoluble ethylenically unsaturated monomer, (c) 0.0001 to 1% copolymerisable polyethylenically unsaturated monomer or other cross linking agent and (d) 1 to 70% of ethylenically unsaturated monomer that carries a pendant group -A m B n ApR wherein B is ethyleneoxy, n is an integer of at least 2, A is propyleneoxy or butyleneoxy, m and p are each an integer less than n and preferably below 2 and most preferably zero, and R is a hydrophobic group containing at least 8 carbon atoms. Throughout this specification all percentages are by weight unless otherwise specified.
  • R can be a polyoxyalkylene chain where the alkylene groups wholly or mainly are propylene or higher but preferably is a hydrocarbyl group.
  • the hydrocarbyl group generally contains from 8 to 30, preferably 10 to 24 and most preferably 12 to 18 carbon atoms. It may be selected from alkyl, for instance octyl, lauryl or stearyl, aralkyl such as 2-phenyl-ethyl (-C 2 H 4 Ph), aryl such as naphthyl, alkaryl such as alkyl phenyl wherein the alkyl group generally contains 6 to 12 carbon atoms, cycloalkyl (including polycyclic alkyl groups), or mixtures of one or more such groups.
  • Preferred hydrocarbyl groups are alkyl and alkaryl groups. Any of these groups may additionally be substituted provided the substituents do not render the pendant group hydrophilic to an extent that the desired improvement in properties due to the hydrophobic group is lost.
  • the polyoxyethylene chain (ns2) may be interrupted by oxypropylene groups but preferably m and p are each zero.
  • the properties of the final polymer can be controlled by appropriate selection of n, m, p and R.
  • the amount of monomer (d) is generally from 3 to 50% by weight, often 3 to 30%.
  • the polymers surprisingly have very good absorptive capacity for electrolytes and that it is possible to obtain an excellent combination of absorptive capacity and non-tackiness for aqueous media in general, and especially for aqueous electrolytes.
  • n is at least 5 and most preferably at least 10 with best results generally being obtained when it is 10 or more, e.g., up to 20 or 50 or even 100.
  • the hydrophobic group can therefore be introduced as, for instance, an acrylic ester of a surfactant alcohol or other group described in the patents listed above, but preferably the hydrophobic group is introduced as an allyl ether of a surfactant alcohol.
  • the allyl ethers may be made by methods such as those described in GB 1,273,552, for instance by reacting an appropriate surfactant alcohol with sodium or sodium alkoxide, generally in the absence of water but in a solvent such as xylene, to form the sodium derivative and then reacting this with allyl chloride, or by reacting allyl alcohol with the surfactant alcohol with or without catalyst.
  • the allyl ethers are made by the method described in our copending application inventors Farrar and Hawe, filed even date herewith reference 60/2566.
  • Water insoluble monomer (b) may be present, for instance to control the degree of swelling of the polymer, in amounts up to 40% but the amount is generally below 20% and it is generally best for the polymer to be free of water insoluble monomer.
  • water insoluble monomer in this specification we mean a monomer soluble in water to the extent of less than 5% at room temperature. If such monomer is to be incorporated then it may be, for instance, styrene, acrylonitrile, vinyl chloride or vinyl acetate but is preferably an alkyl, hydroxy alkyl or alkoxy alkyl (meth) acrylate most preferably a C 1-4 alkyl (meth) acrylate.
  • the water soluble monomer (a) can be a single monomer or a monomer blend and the monomers may be cationic, non-ionic or anionic and are usually vinyl monomers, especially acrylic monomers.
  • Monomer (a) often comprises 20 to 100% ionic monomer and 0-80% non-ionic monomer, the amounts being based on the weight of monomer (a).
  • Other suitable cationic monomers that may be used include dialkylaminoalkyl (meth) acrylamides where the aminoalkyl group generally includes an alkylene group of 2 to 8 carbon atoms, preferably 1,3-propylene, e.g., dimethylamino-1,3-propylene methacrylamide.
  • Cationic monomers are usually used blended with 20 to 95%, generally 60 to 95%, non-ionic monomer by weight of the blend of water soluble monomers).
  • the preferred anionic monomers are ethylenically unsaturated carboxylic and sulphonic acids, generally as water soluble salts such as the sodium salt. Suitable acids are allyl sulphonic acid, 2-acrylamido-2-methyl propane sulphonic acid, methacrylic acid, itaconic acid, crotonic acid or, preferably, acrylic acid.
  • the water soluble monomer consists only of anionic monomer, for instance sodium acrylate, but in many polymers the anionic monomer is blended with a non-ionic monomer, the amount of non-ionic monomer in the blend generally being from 2 to 80%, often 30 to 70% by weight of the blend.
  • Non-ionic monomer can be used by itself, but generally in combination with cationic or anionic monomer.
  • the preferred non-ionic monomer is acrylamide.
  • One preferred group of polymers are terpolymers of 3 to 30% of the allyl ether or other monomer carrying the hydrophobe, 20 to 60% by weight of a monomer selected from dialkylamino alkyl (meth)-acrylates and -acrylamides and their acid salts and quaternised derivatives where the alkyl groups contain up to 4 carbon atoms, and sodium acrylate and 30 to 70% acrylamide.
  • Another preferred group of polymers are formed from 3 to 30% of the allyl ether or other group carrying the hydrophobe and 97 to 70% by weight of a monomer selected from dialkylamino alkyl (meth)-acrylates and -acrylamides and their acid salts and quaternised derivatives where the alkyl groups contain up to 4 carbon atoms, and sodium acrylate and 0 to 20% acrylamide.
  • a monomer selected from dialkylamino alkyl (meth)-acrylates and -acrylamides and their acid salts and quaternised derivatives where the alkyl groups contain up to 4 carbon atoms, and sodium acrylate and 0 to 20% acrylamide.
  • polymers are terpolymers of 3 to 30% monomer (d), usually an allyl ether, 20 to 60% dialkylaminoalkyl (meth)-acrylate or dialkylaminoalkyl (meth)-acrylamide or acid salt or quaternised derivatives where the alkyl groups contain up to 4 carbon atoms with 30-70% acrylamide.
  • Polymers containing cationic groups are particularly useful where the fluid to be absorbed contains multivalent metal ions.
  • cross linking agents typically used for cross linking water swellable polymers may be used.
  • a typical polyethylenically unsaturated monomer is methylene bis acrylamide.
  • Ionic cross linking agents can be used, e.g., aluminium sulphate.
  • the amount of cross linking agent is generally below 1% and preferably is below 0.5%, most preferably below 0.2%. It is usually at least 0.0005%, preferably at least 0.01. amounts of 0.0005 to 0.1% are often preferred.
  • the amount of cross linking agent is preferably such that the polymer has an absorptive capacity for deionised water of from 50 to 1000 ml per gram dry polymer, and an absorptive capacity for the aqueous phase that it is to absorb of at least 30 and preferably at least 100.
  • the polymer may be made by gel polymerisation followed by drying and comminution in conventional manner or as described in EP 0 169 674. Alternatively the polymer may be made by reverse phase bead polymerisation, followed by azeotropic distillation and filtration in conventional manner.
  • the dry particle size is generally from 50 to 2000 J.Lm, preferably 100 to 1000 J.Lm, e.g., 200 to 700 J.Lm.
  • the dry particle size is the size of the particles when substantially dry, i.e., when dried to ambient atmospheric moisture content.
  • the polymerisation conditions are preferably such that if the polymer was made under the identical conditions but free of cross linker it would have IV (single point intrinsic viscosity measured in sodium chloride at 25 ° C at 0.05% polymer concentration) of at least 1, generally at least 2 and usually at least 3, for instance 5 to 10 or even higher, for instance up to 20 or more such as are typically obtainable from the monomers (a) and (b) in the absence of (c) and (d).
  • IV single point intrinsic viscosity measured in sodium chloride at 25 ° C at 0.05% polymer concentration
  • the surface of the particles is preferably less swellable than the inner parts of the particles, preferably as a result of cross linking the surface layer. This treatment can reduce the stickiness of the particles and can improve the absorption properties, especially when the polymer contains at least 70% of an anionic monomer.
  • cross linking can be achieved by contacting the surfaces of the particles with a polyvalent metal salt or other cross linking agent.
  • a polyvalent metal salt or other cross linking agent For instance in U.S. 3,114,651 and 3,251,814 particles are treated with a chromic salt.
  • JP 1983/42602 an insoluble water absorbent cross linked polymer is dispersed in a medium containing polyvalent metal salt or epihalohydrin.
  • Other methods and materials are described in U.S. 4,043,952 and 4,090,013.
  • Another method comprises coating anionic particles with a cationic polymer, such as a polymer of diallyl dimethyl ammonium chloride, e.g., during comminution of the polymer.
  • a cationic polymer such as a polymer of diallyl dimethyl ammonium chloride
  • the absorbent polymers can be used in any environment where an aqueous medium is to be absorbed, e.g., wherever cross linked swellable particles of sodium polyacrylate (optionally copolymerised with acrylamide) have been used previously. They are of particular value when the medium contains an electrolyte.
  • the presence of the pendant hydrophobic group greatly improves the absorptive capacity of aqueous electrolytes compared to the corresponding polymers free of such groups.
  • the polymers are generally used in a situation that they absorb all the free fluid and so are not surrounded by a continuous aqueous phase but are instead surrounded by, for instance, air.
  • the invention includes processes in which the polymer particles are used as absorbents as well as compositions and other products in which they are acting as absorbents.
  • the polymers are of particular value as absorbents in diapers and may be incorporated in them in conventional manner and in conventional amounts.
  • the particles can also be used as absorbents in other personal hygiene absorbent products, such as bandages. They can be used for dewatering slurries or for the other purposes described in EP 86301521.0. They can be used for conditioning soil or for promoting growth characteristics of soil or other culture medium, for instance as described in EP 0101253. They can be used as a diverter for preflush and acidising applications downhole..
  • the amount of polymer will be selected having regard to the absorptive capacity of the polymer for the particular aqueous medium that is to be absorbed. Generally the polymer will be present in an amount 0 to 100% above the amount required for absorption of all the aqueous medium.
  • a range of polymers were made by gel polymerisation using differing amounts of acrylamide, sodium acrylate, allyl ether and cross linking agent, and by using different monomers (d) which are all allyl ethers.
  • the product of the polymerisation was then dried and comminuted to give particles having sizes in the range 200 to 500 1 1m.
  • Comparison of polymers 3 and 4 shows the advantage that follows from increasing the length of the ethoxy chain. Very poor results are obtained when there is no ethoxy chain, as in U.S. 4,190,562.
  • Example 1 can be repeated except that the allyl ether is omitted and is replaced by either a diester formed between itaconic acid and the corresponding ethoxylate of stearyl alcohol or by the monoester formed between acrylic acid and the ethoxylate of stearyl alcohol.
  • example 1 The process of example 1 can be repeated except that the particles can be sprayed with aqueous aluminium sulphate solution and then allowed to dry, before being used as absorbents.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Hematology (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Epidemiology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Absorbent Articles And Supports Therefor (AREA)

Claims (10)

1. Absorbierendes Polymer, das wasserunlösliche, wasserquellbare Teilchen mit einer Größe von mindestens 20 J.Lm im trockenen Zustand umfaßt und welches aus Monomeren gebildet ist, die
(a) 30 bis 99 Gew.-% wasserlösliches, ethylenisch ungesättigtes Monomer,
(b) 0 bis 40 Gew.-% wasserunlösliches, ethylenisch ungesättigtes Monomer und
(c) 0,01 bis 1 Gew.-% Vernetzungsmittel
umfassen, und welches dadurch gekennzeichnet ist, daß die Monomeren 1 bis 70 Gew.-% ethylenisch ungesättigtes Monomer (d) umfassen, welches eine -AmBnApR-Seitengruppe aufweist, worin B Ethylenoxy ist, n mindestens 2 ist, A Propylenoxy oder Butylenoxy ist, m und p jeweils ganze Zahlen mit einem Wert kleiner als n sind und R eine hydrophobe Gruppe ist, die mindestens 8 Kohlenstoffatome enthält.
2. Polymer nach Anspruch 1, in dem n mindestens 5, vorzugsweise 10 bis 100 ist und m und p jeweils 0 sind.
3. Polymer nach Anspruch 1 oder 2, in dem R Polyoxypropylen, Polyoxybutylen oder eine Kohlenwasserstoffgruppe mit 8 bis 30 Kohlenstoffatomen, welche ausgewählt ist aus Alkyl, Aralkyl, Aryl, Alkaryl und Cycloalkyl, darstellt.
4. Polymer nach Anspruch 3, in dem R eine Kohlenwasserstoffgruppe mit 10 bis 24 Kohlenstoffatomen darstellt und ausgewählt ist aus Alkyl und Alkaryl.
5. Polymer nach Anspruch 1, in dem das Monomere (d) der Formel CH2=CR'CH20AmBnApR entspricht, worin R' Wasserstoff oder Methyl ist.
6. Polymer nach einem der vorhergehenden Ansprüche, in dem das Monomere (a) 20 bis 100% ionisches Monomer mit 0 bis 80% nicht-ionischem Monomer umfaßt, wobei die Mengen auf das Gewicht des Monomers (a) bezogen sind.
7. Polymer nach einem der vorhergehenden Ansprüche, in dem das Monomere (a) 20 bis 100% eines Monomers umfaßt, welches ausgewählt ist aus Dialkylaminoalkyl (meth)-acrylaten und -acrylamiden und deren Säuresalzen und quatemisierten Derivaten, wobei die Alkylgruppen bis zu 4 Kohlenstoffatome enthalten, und Natriumacrylat mit 0 bis 80% Acrylamid.
8. Polymer nach einem der vorhergehenden Ansprüche, umfassend 3 bis 30 Gew.-% des Monomers (d), 20 bis 60 Gew.-% eines Monomers, welches ausgewählt ist aus Dialkylaminoalkyl (meth)-acrylaten und -acrylamiden und deren Säuresalzen und quaternisierten Derivaten, wobei die Alkylgruppen bis zu 4 Kohlenstoffatome enthalten, und Natriumacrylat, und 30 bis 70 Gew.% Acrylamid und 0,0005 bis 0,1% Vemetzungsmittel.
9. Polymer nach einem der Ansprüche 1 bis 6, hergestellt aus 3 bis 30 Gew.-% des Monomers (d), 97 bis 70 Gew.-% eines Monomers, welches ausgewählt ist aus Dialkylaminoalkyl (meth)-acrylaten und -acrylamiden und deren Säuresalzen und quaternisierten Derivaten, wobei die Alkylgruppen bis zu 4 Kohlenstoffatome enthalten, und Natriumacrylat, und 0 bis 20 Gew.-% Acrylamid und 0,0005 bis 0,1% Vernetzungsmittel.
10. Windel, die ein absorbierendes Polymer nach Anspruch 1 enthält.
EP86306076A 1985-08-12 1986-08-06 Absorbierende Polymere, deren Herstellung und Verwendung Expired EP0213799B1 (de)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
GB858520218A GB8520218D0 (en) 1985-08-12 1985-08-12 Polymers
GB8520218 1985-08-12
GB8603654 1986-02-14
GB8603654 1986-02-14

Publications (2)

Publication Number Publication Date
EP0213799A1 EP0213799A1 (de) 1987-03-11
EP0213799B1 true EP0213799B1 (de) 1990-04-04

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ID=26289653

Family Applications (1)

Application Number Title Priority Date Filing Date
EP86306076A Expired EP0213799B1 (de) 1985-08-12 1986-08-06 Absorbierende Polymere, deren Herstellung und Verwendung

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EP (1) EP0213799B1 (de)
CA (1) CA1286445C (de)
DE (1) DE3670087D1 (de)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5280079A (en) * 1986-11-20 1994-01-18 Allied Colloids Limited Absorbent products and their manufacture
CA1286465C (en) * 1986-11-20 1991-07-23 Adrian Swinburn Allen Absorbent polymeric materials and their manufacture
CA1329305C (en) * 1986-11-20 1994-05-03 Adrian Swinburn Allen Absorbent polymeric materials and their manufacture
GB8910788D0 (en) * 1989-05-10 1989-06-28 Allied Colloids Ltd Absorbent products and their manufacture
EP0277017A3 (de) * 1987-01-30 1989-01-25 Ciba Specialty Chemicals Water Treatments Limited Kohlezusammensetzung und seine Herstellung
DE3925220C1 (de) * 1989-07-29 1991-01-03 Th. Goldschmidt Ag, 4300 Essen, De
GB2340835B (en) 1998-08-26 2003-01-15 Pvax Ploymers Ltd PVA-containing compositions
US6213416B1 (en) 1998-09-28 2001-04-10 Ciba Specialty Chemicals Water Treatments Ltd. Treatment of phosphate-containing rock
US6565981B1 (en) 1999-03-30 2003-05-20 Stockhausen Gmbh & Co. Kg Polymers that are cross-linkable to form superabsorbent polymers
GB0005016D0 (en) 2000-03-01 2000-04-26 Jumik Technologies Limited PVA-Containing compositions
EP1160197A1 (de) * 2000-05-29 2001-12-05 Ciba Specialty Chemicals Water Treatments Limited Behandlung von Phosphatgestein

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1263148A (en) * 1968-04-03 1972-02-09 Toray Industries Antistatic copolymers and their use in the treatment of synthetic fibers
DE2758122A1 (de) * 1977-12-24 1979-07-05 Basf Ag Wasserloesliche copolymerisate auf der basis von hydrophilen aethylenisch ungesaettigten monomeren
US4384096A (en) * 1979-08-27 1983-05-17 The Dow Chemical Company Liquid emulsion polymers useful as pH responsive thickeners for aqueous systems

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CA1286445C (en) 1991-07-16
DE3670087D1 (de) 1990-05-10
EP0213799A1 (de) 1987-03-11

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